A cross-substrate silane crosslinking flexible sealant filling composition and application thereof

Abstract

The present application belongs to the technical field of compressed air energy storage power station engineering materials and underground engineering sealing, and specifically provides a composition containing a miniemulsion polymer emulsion for compressed air energy storage, the composition forms a closed gas storage space through sealing and / or filling, and more specifically, the polymer forms a flexible, air impermeable, dense and continuous sealing material or sealing layer between the same substrate or across substrates. The composition has excellent interfacial bonding capacity for different substrates, and can maintain continuous bonding and sealing when relative displacement occurs due to the difference in thermal expansion of different substrates. In addition, a continuous and dense barrier is formed after curing, which can simultaneously achieve "deep plugging + surface air tightness", thereby adapting to the sealing of underground scenes and key weak positions. Therefore, the composition of the present application has a wide application prospect in the field of sealing and filling of the gas storage space of compressed air energy storage.

Description

Technical Field

[0001] This invention belongs to the field of compressed air energy storage power station engineering materials and underground engineering sealing technology, specifically relating to a composition for compressed air energy storage that forms a closed gas storage space through silane cross-linking flexible sealing and / or filling, as well as a sealing and filling method and a cross-substrate sealing and filling structure based on the composition. Background Technology

[0002] As a large-scale, long-life, physical form of energy storage technology, compressed air energy storage (CAES) is considered one of the most promising long-term energy storage technologies. In the construction of a CAES system, the construction cost of the gas storage device (gas storage tank) accounts for approximately 30% to 60% of the total cost, and its airtightness and structural stability directly determine the operating efficiency and safety of the power plant.

[0003] Due to geographical limitations, natural salt cavern resources are unevenly distributed and limited in my country. Therefore, constructing non-salt cavern gas storage facilities using artificial chambers (such as lined rock caverns), abandoned mine tunnels, or urban underground spaces has become an important development direction. However, unlike salt caverns which rely on the density and creep self-healing properties of rock salt, non-salt cavern gas storage facilities typically employ a composite structure of "surrounding rock + concrete lining + sealing layer (or steel plate)". In actual operation, this composite structure faces extremely harsh working conditions: Temperature-pressure coupling and differential expansion: Cyclic inflation and deflation cause periodic changes in temperature and pressure. At the interface, it is more likely to experience alternating tension and compression, shear slip, and relative displacement caused by thermal expansion differences. Conventional rigid materials are prone to cracking or interface debonding, while flexible materials may have problems with insufficient heat resistance, pressure resistance, and long-term creep control.

[0004] The challenge of coordinated deformation at multi-substrate interfaces: CAES gas storage spaces often contain a combination of multiple media such as metal linings / components, concrete linings, surrounding rock, and anti-corrosion coatings. Typical weak points are concentrated in the steel-concrete transition zone, the root of the through-wall pipe, construction joints / deformation joints, and the surrounding rock disturbance and fracture zone. A single material often cannot achieve "high adhesion + low permeability + high deformation follow-up" at the same time between different substrates.

[0005] Balancing microfracture penetration sealing with long-term stability: Leakage channels such as surrounding rock fissures / joints and lining-surrounding rock interfaces are characterized by large scale spans, irregular shapes, and complex connection paths. Materials need to have the ability to be injected and permeate and solidify in situ during the construction period, and to resist high-frequency cycling and long-term aging effects during the service period.

[0006] Existing sealing technologies have significant limitations in addressing the above challenges: Traditional cement-based grouting materials: Although they are low in cost and high in strength, they are inherently brittle materials with low tensile strength. They are difficult to adapt to high-frequency "breathing" deformation and are prone to microcracks in stress concentration areas, leading to airtightness failure.

[0007] Ordinary organic coatings (such as epoxy resin and polyurethane): Ordinary epoxy resin has high rigidity and lacks flexibility after curing, and is prone to brittleness at low temperatures; while conventional polyurethane, although flexible, has poor adhesion to damp substrates (such as seepage rock walls commonly found in underground engineering) and is prone to interfacial delamination.

[0008] Conventional polymer emulsions: Although environmentally friendly in construction, the particles prepared by conventional emulsion polymerization are relatively large (usually greater than 500nm), making it difficult to penetrate into micro-cracks (<100nm) or the capillaries of dense concrete; moreover, conventional emulsion films have poor water resistance and high-pressure gas permeability resistance. More importantly, conventional emulsions mainly rely on physical deposition to form films, lacking chemical cross-linking and densification, making them prone to creep under long-term high pressure.

[0009] Therefore, existing technologies urgently need a sealing and filling material system for CAES gas storage spaces: firstly, capable of achieving stable and continuous bonding and sealing between different substrates (such as metal / concrete / rock / coating); secondly, possessing deformation adaptability and interface retention capabilities under cyclic temperature and pressure changes to avoid through cracking or interface debonding that could lead to interconnected leakage channels; and thirdly, possessing both injectable penetration and in-situ curing characteristics to adapt to the deep sealing requirements of micro-cracks and porous media. Summary of the Invention

[0010] To address the above problems, the present invention provides the following technical solution.

[0011] (a) Silane crosslinked flexible sealing and filling composition The present invention provides a use of a composition in compressed air energy storage, wherein the composition is cross-linked with silane to form a flexible, airtight, dense, and continuous sealing material or sealing layer to seal the air storage space, forming a closed air storage space, and wherein the composition comprises a fine emulsion polymer emulsion.

[0012] The fine emulsion polymer emulsion comprises polymer particles dispersed in an aqueous phase. These polymer particles are copolymerized from acrylate monomers, styrene monomers, and silane monomers containing hydrophobic long chains in the presence of a hydrophobic co-stabilizer, and can form core-shell or gradient structures. The polymer particle molecular chains possess hydrolyzable alkoxysilane functional groups, which, upon curing, form a silane crosslinking network containing Si-O-Si bonds. This crosslinking network can be a room-temperature self-crosslinking or a moisture-curing crosslinking structure.

[0013] To ensure that the cured sealing layer exhibits deformation adaptability under alternating temperatures, the present invention preferably controls the glass transition temperature (Tg) of the polymer between -40°C and 30°C.

[0014] To balance infiltration and stable film formation, this invention preferably controls the median particle size D50 of the polymer particles to be between 100 nm and 500 nm, and the PDI to be no greater than 0.25.

[0015] Furthermore, the composition of the present invention may include an inorganic filler modified with a silane coupling agent, which allows the surface groups of the inorganic filler to chemically bond with the alkoxysilane functional groups on the polymer particles, thereby improving heat resistance and reducing gas permeability. Preferably, the inorganic filler includes at least one of quartz powder, microsilica powder, flaky mica, fly ash, or nanoclay.

[0016] In a preferred embodiment, the composition is cured to form a flexible sealing material or sealing layer for filling and / or sealing leak channels, and can achieve adhesive sealing at the interface of the same substrate or different substrates.

[0017] In a preferred embodiment, the curing includes hydrolysis and condensation reactions of alkoxysilane functional groups, forming a silane crosslinking network containing Si-O-Si bonds in the flexible sealing layer. Preferably, the crosslinking network is a room temperature self-crosslinking and / or moisture-curing crosslinking structure.

[0018] In a preferred embodiment, the alkoxysilane functional group is introduced by a polymerizable silane monomer; the polymerizable silane monomer includes N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, which also acts as a reactive co-stabilizer during the preparation of the fine emulsion.

[0019] In a preferred embodiment, the substrate is selected from the group consisting of: metals (steel / iron), concrete, rock (granite / basalt / sandstone) and organic anti-corrosion coatings.

[0020] In a preferred embodiment, the interface between different substrates is the interface between at least two different substrates that are adjacent or overlapped within the area to be sealed, and the thermal expansion coefficients of the at least two substrates are different. Preferably, the substrates include at least two of the following: metal (steel / iron), concrete, rock mass (granite / basalt / sandstone), and organic anti-corrosion coating.

[0021] In a preferred embodiment, the cured flexible sealing material or sealing layer has one or more of the following properties to resist temperature changes and deformations caused by compressed air inflation and deflation: (a) Elongation at break ≥ 150%, preferably ≥ 200%; (b) The bond strength with both concrete and metal substrates is ≥1.5 MPa, preferably ≥2.0 MPa, and more preferably ≥2.5 MPa; (c) After undergoing at least 50 cycles of high and low temperatures from -20°C to 80°C, the interface does not develop through cracks or leak channels caused by interface debonding.

[0022] (ii) Sealing and / or filling methods This invention provides a method for sealing a compressed air energy storage space, comprising: (1) Pre-treatment of the sealing area, including cleaning, degreasing and / or interface treatment; (2) Apply the above-mentioned sealing and filling composition to the part to be sealed, seal and / or fill the part to be sealed, and cure in situ to form a flexible sealing material or sealing layer to block or block the part to be sealed.

[0023] In a preferred embodiment, the part to be sealed is a weak point in the airtight layer, which may include: cracks, joints, porous media, interfaces, voids, cavities, lining interfaces, and sleeve interfaces.

[0024] Specifically, when the gas storage space to be sealed is a tunnel or artificial chamber, the key areas to be sealed include: cracks in the lining, surrounding rock, pipes, and interfaces themselves, or gaps between them and other structures; voids and cavities between the tunnel's open face, arch, primary lining, secondary lining, and surrounding rock.

[0025] When the gas storage space to be sealed is a mine, oil and gas well, gas storage well, or mine roadway, the part to be sealed includes: cracks in the multi-layer casing or cement sheath itself or gaps with other structures; the interface between the casing and the cement sheath; and the annulus between the multi-layer casings.

[0026] In a preferred embodiment, the area to be sealed includes the steel-concrete transition zone, the root of the through-wall pipe, the construction joint / deformation joint, and the surrounding rock disturbance fracture zone.

[0027] For micro-cracks or porous media, a pressure grouting or spraying process of 0.5MPa to 5.0MPa is preferred, so that the fine emulsion polymer emulsion in the sealing and filling composition can penetrate into the depth of the pores by taking advantage of its low viscosity and small particle size characteristics.

[0028] For gaps, voids, and cavities between interfaces, a direct filling method is preferred to form a dense sealing layer between the two interfaces to seal and block the parts to be sealed.

[0029] Furthermore, a gradient sealing process is preferred: first, a low-solids, low-viscosity fine emulsion is applied as a penetrating primer to wet the capillaries and anchor them; then, a high-solids or filler-containing sealing and filling composition is applied as a film-forming topcoat to form a dense, airtight barrier.

[0030] In a preferred embodiment, step (2) includes the following steps: A composition comprising a polymer emulsion is applied to microcracks and / or porous media by means of grouting, spraying and / or scraping, thereby sealing the microcracks and / or porous media.

[0031] In a preferred embodiment, step (2) includes the following steps: A composition containing a polymer emulsion is injected directly between two interfaces where there are voids, cavities, or annular spaces to form a dense sealing layer and seal the gas storage space.

[0032] In a preferred embodiment, step (2) employs a gradient sealing process: First, a low-solids-content, low-viscosity fine emulsion polymer emulsion is applied as a penetrating primer to wet the capillaries of the substrate and anchor it; Second, a high-solids-content or filler-containing sealing and filling composition is applied as a film-forming topcoat to form a dense, airtight barrier.

[0033] (iii) Cross-substrate sealing and filling structure The present invention also provides a cross-substrate sealing and filling structure for compressed air energy storage space, including a first substrate, a second substrate, and a sealing layer connecting the two; the sealing layer is formed by curing the above-mentioned sealing and filling composition, and tightly connects the first substrate and the second substrate through siloxane chemical bonds and / or physical anchoring, forming a continuous airtight barrier that can adapt to periodic expansion and contraction deformation.

[0034] The structure is suitable for the overlapping edges of multiple materials such as metal-concrete-coating, the interface between lining and surrounding rock, and airtight weak links such as cracks / joints in surrounding rock. It is also suitable for key areas such as the transition zone between steel lining and concrete, the root of pipes penetrating through walls, construction joints / deformation joints and the surrounding rock disturbance and crack zone.

[0035] In a preferred embodiment, the sealing layer spans the metal-concrete-coating multi-material overlap edge and covers the lining-surrounding rock interface and / or surrounding rock fissures / joints to reduce the connectivity of interface leakage channels.

[0036] In a preferred embodiment, the gas storage space is a non-salt cavern underground gas storage space, including artificial chambers, lined tunnels, urban underground spaces, or abandoned mine tunnels.

[0037] In a preferred embodiment, the sealing and filling composition and structure are suitable for use and maintaining an hermetically tight seal under one or more of the following operating conditions: (a) Operating pressure fluctuation range: 6 MPa ~ 25 MPa; (b) Pressure change rate: ≥0.1 MPa / min; (c) Cycle life: ≥ 20,000 charge-discharge cycles.

[0038] Compared with the prior art, the present invention has at least the following beneficial effects (not limited thereto): Cross-substrate bonding and airtight integration: By forming a Si-O-Si cross-linked network under room temperature / humid conditions through hydrolyzable alkoxysilane functional groups, and undergoing silanization / bonding with hydroxyl groups on the substrate surface, the interfacial bonding and retention capabilities of different substrates such as metals, concrete, rock and coatings are significantly improved.

[0039] Strong temperature and deformation coordination: The Tg (-40℃~30℃) design endows the sealing layer with viscoelasticity and deformation adaptability under alternating temperatures, so that it can maintain continuous bonding and sealing even when the thermal expansion difference of different substrates causes relative displacement, reducing the risk of through cracking / interface debonding leading to the connection of leakage channels.

[0040] It combines penetration and sealing with dense film formation: the fine emulsion has a small particle size and narrow distribution, which is conducive to deep penetration of microcracks / porous media; after curing, it forms a continuous and dense barrier, which, together with the sealing process, can achieve "deep sealing + surface airtightness" at the same time.

[0041] Enhanced heat resistance and low permeability: The introduction of inorganic fillers modified with silane coupling agents can construct an organic-silicon-oxygen-inorganic composite network through chemical bonding, thereby improving heat resistance and reducing gas permeability to meet the long-term service requirements of high-pressure gas storage.

[0042] Adaptable to non-salt cavern underground scenarios and key vulnerable areas: Applicable to the treatment of typical vulnerable areas in non-salt cavern underground gas storage spaces such as artificial chambers, lined tunnels, urban underground spaces, and abandoned mine roadways. Attached Figure Description

[0043] Figure 1 The tensile shear strength results for different substrates are shown.

[0044] Figure 2A The tensile stress-strain curve (type 2 dumbbell) is shown.

[0045] Figure 2B The data consistency results of the tensile test are shown.

[0046] Figure 3A The results show the evolution of mechanical properties during UV aging.

[0047] Figure 3BThe study shows the performance retention rate and color difference evolution trend during UV aging. Detailed Implementation

[0048] Through extensive and in-depth research, the inventors have discovered for the first time a composition containing a fine emulsion polymer emulsion for cross-substrate silane crosslinking flexible sealing and filling, wherein the composition, after curing, forms a silane crosslinking network containing Si-O-Si bonds.

[0049] The composition exhibits excellent interfacial adhesion to different substrates and maintains continuous adhesion and sealing even when relative displacement occurs due to differences in thermal expansion between the substrates. After curing, the composition forms a continuous and dense barrier, achieving both deep sealing and surface airtightness, thus making it suitable for non-salt cavern underground scenarios and critical weak points.

[0050] Based on this, the present invention was completed.

[0051] the term Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0052] As used herein, the terms “comprising,” “including,” and “containing” are used interchangeably and include not only closed definitions but also semi-closed and open definitions. In other words, the terms include “consisting of” and “substantially consisting of”.

[0053] As used herein, when referring to a specific enumerated value, the term “about” means that the value can vary by no more than 1% from the enumerated values. For example, as used herein, the expression “about 100” includes all values ​​between 99 and 101 (e.g., 99.1, 99.2, 99.3, 99.4, etc.).

[0054] Compressed gas energy storage Compressed air storage is a large-scale energy storage technology that converts electrical energy into the pressure energy of high-pressure air for storage, and then converts the pressure energy back into electrical energy when electricity is needed.

[0055] Compressed gas storage requires a large space to store high-pressure air. Due to cost considerations, these spaces are usually abandoned tunnels, artificial chambers, abandoned mines, abandoned oil and gas wells, or subsea tanks. However, these abandoned large spaces often have problems such as poor airtightness, aging structures, and inability to withstand repeated filling and discharging of high-pressure gas. Therefore, sealing materials are needed to seal the gas storage space.

[0056] The sealing material not only needs to have excellent conventional airtightness, but also requires even higher airtightness under high-pressure conditions because compressed gas storage deals with high-pressure gas and will undergo multiple cycles of high-pressure gas storage and release.

[0057] In addition, sealing materials usually need to seal and bond different materials such as surrounding rock, concrete, and steel plates. Therefore, higher requirements are needed for cross-substrate bonding ability. Similarly, it needs to adapt to the expansion and contraction of the gas storage space that may be caused by multiple cycles of high-pressure gas storage and release. Therefore, the above-mentioned large gas storage space needs to be flexibly sealed to form a flexible sealing layer.

[0058] polymer emulsion As used herein, the terms “fine emulsion polymer” and “polymer emulsion” are used interchangeably.

[0059] The polymer emulsion of the present invention has excellent adhesive properties after curing, and can bond across multiple materials, enabling bonding at the interface of different substrates such as metal, concrete, rock and coating.

[0060] Furthermore, the polymer emulsion of the present invention, through the design of Tg, endows the cured material with viscoelasticity and deformation adaptability under alternating temperatures, so that it can still maintain continuous adhesion and sealing when the thermal expansion difference of different substrates causes relative displacement, thereby reducing the risk of through cracking / interface debonding leading to the connection of leakage channels.

[0061] The polymer emulsion of the present invention has a small emulsion particle size and narrow distribution, which is conducive to deep penetration of microcracks / porous media; and it can directly fill the space between two interfaces, effectively avoiding interlayer gas leakage, and simultaneously solving the gaps that may exist between the two interfaces. After curing, it forms a continuous and dense airtight layer, thereby achieving "deep sealing + surface airtightness" at the same time.

[0062] The polymer emulsion of the present invention also has excellent weather resistance after curing, and will not age or crack after long-term use.

[0063] In this invention, a high-HLB EO-PO-EO block copolymer is used as the main emulsifier, combined with a specific silane monomer (e.g., N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane) that simultaneously possesses the triple functions of "stabilizing agent / polymerizable / coupling agent" as a stabilizer and functional monomer. The emulsion is prepared by copolymerizing acrylate monomers, styrene monomers and the above-mentioned silane monomer in the presence of the above-mentioned silane monomer as a stabilizer. The pre-emulsion droplet size (e.g., D50 about 300–1000 nm, PDI ≤ 0.18) is precisely controlled by high-pressure homogenization to obtain the polymer emulsion of this invention.

[0064] The fine emulsion polymer emulsion comprises polymer particles dispersed in an aqueous phase. These polymer particles are copolymerized from acrylate monomers, styrene monomers, and silane monomers containing hydrophobic long chains in the presence of a hydrophobic co-stabilizer, and can form core-shell or gradient structures. The polymer particle molecular chains possess hydrolyzable alkoxysilane functional groups, which, upon curing, form a silane crosslinking network containing Si-O-Si bonds. This crosslinking network can be a room-temperature self-crosslinking or a moisture-curing crosslinking structure.

[0065] Preferably, the method for preparing the polymer emulsion includes the following steps: (1) The conventional monomer and the functional monomer are premixed evenly. Under stirring, the monomer mixture is added to deionized water in which the main emulsifier is dissolved to form a pre-emulsion, wherein: - The main emulsifier is an EO-PO-EO block copolymer with a molecular weight of 8000-14000 Da and an HLB value ≥18; - The functional monomer simultaneously functions as a co-stabilizer, silane coupling agent, and reactive monomer, possessing the triple functions of "co-stabilizer / polymerizable / coupling". It is N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, and its addition amount is 0.5-10% of the total monomer weight. (2) The pre-emulsion obtained in step (1) is subjected to a high-pressure homogenizer and circulated 2-5 times under a pressure of 50-200 MPa. The median particle size (D50) of the droplets in the pre-emulsion is 400-800 nm and the particle size distribution index (PDI) is ≤0.15. (3) Under nitrogen protection, the pre-emulsion is heated to 70-80℃, an initiator solution is added, and a fine emulsion polymerization reaction is carried out for 4-8 hours to obtain a polymer emulsion with a glass transition temperature (Tg) of -10~20℃.

[0066] Fine emulsion polymer emulsions were prepared according to the above method: acrylate monomers and styrene monomers were mixed in a specific ratio to control the Tg between -40℃ and 30℃; hydrophobic long-chain silane functional monomers were added as hydrophobic co-stabilizers, polymerizable silane monomers, and silane coupling agents; after pre-emulsification with emulsifiers, the emulsions were homogenized, refined, and polymerized to obtain the fine emulsion. By adjusting the homogenization energy and the amount of emulsifier / functional monomer, the D50 was controlled between 100nm and 500nm, and the PDI ≤ 0.25.

[0067] Preferably, the conventional monomer is composed of octyl acrylate and styrene, wherein the mass ratio of octyl acrylate to styrene is 3:7 to 7:3, more preferably 4:6 to 6:4.

[0068] Preferably, the amount of the stabilizer added accounts for 0.5-5 wt% of the total monomer (preferably 2-8 wt%).

[0069] Preferably, the amount of the primary emulsifier added is 1-5% of the weight of the monomer mixture.

[0070] Preferably, the initiator is sodium persulfate, and its addition amount is 0.1-2% of the weight of the monomer mixture.

[0071] Preferably, the number average molecular weight (Mn) of the obtained fine emulsion polymer is 50,000-150,000, and the emulsion solid content is 40-45%.

[0072] Preferably, the resulting polymer emulsion has a solid content of about 40 wt%.

[0073] Preferably, the Tg of the polymer emulsion can fall between -9 and 20 °C according to the monomer ratio.

[0074] Increasing the proportion of styrene monomer in step (1) can increase the Tg, thereby improving strength; increasing the proportion of octyl acrylate can improve the flexibility and deformation-following ability of the polymer emulsion, making it suitable for nodes with large vibrations / displacements. Regarding emulsifying / stabilizing components, EO-PO-EO block copolymers (such as Pluronic® F127) are a class of hydrophilic-hydrophobic-hydrophilic triblock nonionic surfactants that can form micelles in the aqueous phase and stabilize the oil / water interface. High HLB block surfactants can stably form submicron-sized droplets under high shear, reducing dependence on small molecule surfactants and mitigating the risk of "migration / precipitation" from the source. Overall, its high HLB and multi-segment structure are beneficial for maintaining interfacial stability and dimensional stability during film formation near different substrates.

[0075] On the other hand, functional monomers, namely stabilizers, reactive monomers and silane coupling agents, can participate in polymerization (“polymerizable”) on one end and contain hydrolyzable silanes (“coupling”) on the other end. They can form durable chemical bridges (such as Si-O-Si bonds) between organic polymers and inorganic substrates rich in hydroxyl groups, significantly improving adhesion reliability and achieving adhesion sealing at interfaces between different substrates, especially at interfaces between two substrates with different coefficients of thermal expansion.

[0076] The polymer particles have hydrolyzable alkoxysilane functional groups on their molecular chains, which, after curing, form a silane crosslinking network containing Si-O-Si bonds.

[0077] The D50 and PDI of the pre-emulsion droplets in step (2) can be selected by adjusting the pressure (50 / 100 / 150 / 200 MPa) and the number of cycles (2 / 3 / 5 times) of the homogenizer.

[0078] In a preferred embodiment, the polymer emulsion is prepared by the following method, comprising the following steps: (s1) Mix conventional monomers with functional monomers, and then add a primary emulsifier solution to obtain a pre-emulsion; The functional monomer serves as a stabilizer, a silane coupling agent, and a reactive monomer, possessing a triple function of "stabilizing / polymerizable / coupling". It is N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane. (s2) The pre-emulsion obtained in step (s1) is homogenized and mixed to obtain a pre-emulsion; (s3) The pre-emulsion obtained in step (s2) is mixed with an initiator and subjected to a fine emulsion polymerization reaction to obtain the fine emulsion polymer.

[0079] In a preferred embodiment, the polymer emulsion is a non-toxic polymer.

[0080] In a preferred embodiment, the polymer emulsion is non-corrosive.

[0081] In a preferred embodiment, the polymer emulsion is an aqueous polymer.

[0082] In a preferred embodiment, the number average molecular weight (Mn) of the polymer emulsion is 20,000-200,000, preferably 50,000-150,000.

[0083] In a preferred embodiment, the polymer emulsion has a solid content of 30%-50%, preferably 40%-45%.

[0084] In a preferred embodiment, the glass transition temperature of the polymer emulsion is -20~30℃, preferably -10~20℃.

[0085] In a preferred embodiment, the conventional monomer comprises octyl acrylate and styrene.

[0086] In a preferred embodiment, the weight ratio of octyl acrylate to styrene is 3:7 to 7:3, for example, 4:6, 1:1, or 6:4.

[0087] In a preferred embodiment, the structure of the functional unit is as follows: .

[0088] In a preferred embodiment, the amount of the functional monomer added is 0.5-10% of the total weight of the monomer, preferably 1-10%, more preferably 2-8%, for example 1%, 3%, 5%.

[0089] In a preferred embodiment, the primary emulsifier is an EO-PO-EO block copolymer.

[0090] In a preferred embodiment, the primary emulsifier is Pluronic® F127.

[0091] In a preferred embodiment, the molecular weight of the primary emulsifier is 5000-15000 Da, preferably 8000-14000 Da, more preferably 10000-13000 Da, for example 12600 Da.

[0092] In a preferred embodiment, the HLB value of the primary emulsifier is ≥18, more preferably ≥20, for example 22.

[0093] In a preferred embodiment, the amount of the primary emulsifier added is 1-10% of the total weight of the monomers, more preferably 2-8%, for example 1%, 3%, or 5%.

[0094] In a preferred embodiment, the primary emulsifier solution is an aqueous solution of the primary emulsifier, such as a deionized aqueous solution.

[0095] In a preferred embodiment, step (s1) includes: mixing a conventional monomer with a functional monomer, and adding an aqueous solution of a primary emulsifier while stirring to obtain a pre-emulsion.

[0096] In a preferred embodiment, in step (s2), the homogenization mixing refers to mixing in a high-pressure homogenizer for 2-8 cycles (preferably 2, 3, 4, or 5 cycles).

[0097] In a preferred embodiment, in step (s2), the homogenization is carried out at 20-300 MPa, preferably 50-200 MPa, for example 50 MPa, 100 MPa, or 150 MPa.

[0098] In a preferred embodiment, the median particle size D of the droplets in the preemulsion 50 The range is between 300-1000 nm, preferably between 400-800 nm, such as 500 nm, 600 nm, and 700 nm.

[0099] In a preferred embodiment, the droplet size distribution index (PDI) in the preemulsion is ≤0.25, preferably ≤0.20, for example 0.18, 0.13, 0.12, 0.11, or 0.1.

[0100] In a preferred embodiment, step (s2) includes: mixing the pre-emulsion obtained in step (s1) 2-8 times using a high-pressure homogenizer at 20-300 MPa to obtain a pre-emulsion.

[0101] In a preferred embodiment, the initiator is a peroxide initiator, preferably selected from the group consisting of sodium persulfate, ammonium persulfate, potassium persulfate, or combinations thereof.

[0102] In a preferred embodiment, the amount of the initiator added is 0.01-1% of the total weight of the monomer, more preferably 0.05-0.8%, even more preferably 0.1-0.5%, for example 0.2%, 0.25%, 0.3%, 0.4%.

[0103] In a preferred embodiment, in step (s3), the initiator is added in two batches.

[0104] In a preferred embodiment, the weight ratio of the first batch of added initiator to the second batch of added initiator is 2:1 to 1:2, preferably 1:1 to 1:2.

[0105] In a preferred embodiment, step (s3) includes: mixing the pre-emulsion obtained in step (s2) with the first batch of initiator, reacting for T1, and then adding the second batch of initiator dropwise, reacting for T2, to obtain the polymer emulsion.

[0106] In a preferred embodiment, in step (s3), the microemulsion polymerization reaction is carried out at 60-90°C, preferably 70-80°C, for example 75°C.

[0107] In a preferred embodiment, in step (s3), the microemulsion polymerization reaction is carried out in a protective atmosphere.

[0108] In a preferred embodiment, the protective gas is selected from the group consisting of nitrogen, helium, and neon.

[0109] In a preferred embodiment, T1 is 2-20 minutes, preferably 5-20 minutes, for example 10 minutes or 15 minutes.

[0110] In a preferred embodiment, T2 is 4-10 hours, preferably 4-8 hours, such as 5 hours, 6 hours, or 7 hours.

[0111] In a preferred embodiment, step (s3) includes: mixing the pre-emulsion obtained in step (s2) with the first batch of initiators under a protective atmosphere at 60-90°C, reacting for 2-20 minutes, and then adding the second batch of initiators dropwise, reacting for 4-10 hours to obtain the polymer emulsion.

[0112] In a preferred embodiment, the polymer emulsion obtained in step (s3) is a polymer emulsion containing polymer particles prepared by a fine emulsion polymerization method.

[0113] Sealing and filling of compressed air energy storage space The present invention provides a use of a composition comprising the above-mentioned polymer emulsion for compressed air energy storage, wherein the composition forms a closed air storage space by sealing and / or filling.

[0114] When a composition containing a polymer emulsion is applied to a poorly airtight gas storage space, it can be cured at room temperature and / or under humid conditions to form a cross-linked network containing Si-O-Si bonds, forming a flexible sealing material or sealing layer and achieving adhesive sealing.

[0115] In a preferred embodiment, the sealant is a sealant on the same substrate or across substrates.

[0116] In a preferred embodiment, the substrate is selected from the group consisting of: metal, concrete, rock, and organic anti-corrosion coatings.

[0117] In a preferred embodiment, the metal includes one or more of steel, stainless steel, and iron.

[0118] In a preferred embodiment, the rock mass includes one or more of granite, basalt, and sandstone.

[0119] In a preferred embodiment, the sealing and / or filling is the formation of a flexible, airtight, dense, continuous sealing material or sealing layer between the same substrate or across substrates.

[0120] In a preferred embodiment, the polymer emulsion content in the composition is at least 1 wt%, preferably at least 5 wt%, and more preferably at least 10 wt%.

[0121] In a preferred embodiment, the composition is cured to obtain the flexible sealing material or sealing layer.

[0122] In a preferred embodiment, the curing is carried out at room temperature (preferably 10-40°C).

[0123] In a preferred embodiment, the curing time depends on the amount of polymer emulsion to be cured. Typically, the curing of a small amount of premixed filler is carried out within one day, or even within a few minutes, for example, 1 min, 2 min, 3 min, 5 min, 10 min, 30 min, 1 h, 2 h, 5 h, 8 h, 16 h, or 24 h.

[0124] In a preferred embodiment, the composition is cured to form a flexible sealing material or sealing layer, and achieves bonding and sealing at the interface of the same or different substrates.

[0125] In a preferred embodiment, the composition is used to fill and / or seal areas with poor airtightness.

[0126] In a preferred embodiment, the composition has no requirements on the surface of the substrate to be bonded, and can bond various substrates with different roughness (smooth or rough), different coefficients of thermal expansion, and different properties. In particular, it can directly bond rock, concrete, metal, etc. with different coefficients of thermal expansion, and will not crack or warp when the temperature and humidity conditions change and the inner and outer substrates expand at different degrees, thus exhibiting deformation adaptability.

[0127] In a preferred embodiment, the interface between different substrates is the interface between at least two different substrates that are adjacent or overlapped within the area to be sealed, and the at least two substrates have different coefficients of thermal expansion. The substrates include at least two of the following: metal (steel / iron), concrete, rock mass (granite / basalt / sandstone), and organic anti-corrosion coating.

[0128] In a preferred embodiment, the gas storage space is a non-salt cavern underground gas storage space, including mines, subsea gas tanks, caves, oil and gas wells, gas storage wells, tunnels, artificial chambers, lined tunnels, urban underground spaces, or abandoned mine roadways.

[0129] In a preferred embodiment, the gas storage space is not limited by conditions such as temperature, humidity, oxygen content, pressure, and temperature difference. The composition can be sealed and filled in gas storage spaces under different humidity (dry or humid), different oxygen content (oxygen-rich or oxygen-deficient), different pressure (high pressure or low pressure), and different opening conditions (closed or open).

[0130] In a preferred embodiment, the poorly airtight area to be sealed includes one or more of the following: voids or gaps between different interfaces, overlaps of different substrates, and gap channels.

[0131] In a preferred embodiment, the overlap of the different substrates includes one or more of the following: a metal-concrete overlap, a steel-concrete transition zone.

[0132] In a preferred embodiment, the gap channel includes one or more of the following: the root of the through-wall pipe, construction joint, expansion joint, disturbance joint, surrounding rock disturbance fissure zone, and damaged gaps in the lining, surrounding rock, pipe, and casing itself.

[0133] In a preferred embodiment, the gap includes a gap that is visible to the naked eye, as well as a tiny crack that is not visible to the naked eye.

[0134] In a preferred embodiment, the size of the gap is at least 1 μm, preferably at least 0.5 μm, and more preferably at least 0.1 μm.

[0135] In a preferred embodiment, the voids and cavities between the different interfaces include: voids and cavities between the surrounding rock and the lining, between the primary lining and the secondary lining, between the secondary lining and the free face, between the two layers of casing, and between the casing and the cement ring.

[0136] In a preferred embodiment, the gas storage space is located in a building environment with long-term pressure fluctuations and / or humid heat cycles.

[0137] In a preferred embodiment, the composition may also contain other additives commonly used in the field of engineering materials.

[0138] In a preferred embodiment, the additives include airtight agents, plasticizers, elastic restorers, antioxidants, weather-resistant agents, or reinforcing agents.

[0139] In a preferred embodiment, the cured flexible sealing material or sealing layer has one or more of the following properties to resist temperature changes and deformations caused by compressed air inflation and deflation: (a) elongation at break ≥ 150%; (b) bond strength with concrete and metal substrates ≥ 1.5 MPa; (c) after undergoing at least 50 cycles of high and low temperatures from -20°C to 80°C, no through cracking or leakage channels caused by interface debonding occur at the interface.

[0140] In a preferred embodiment, the cured flexible sealing material or sealing layer is configured to have excellent airtightness, effectively preventing high-pressure air (typically 10-30 MPa) from penetrating through the gaps and reducing energy loss.

[0141] In a preferred embodiment, the cured flexible sealing layer is configured to achieve an airtightness of level 5 or higher, preferably level 6 or higher, and more preferably level 7, as tested according to GB / T 31433-2015.

[0142] In a preferred embodiment, the cured flexible sealing layer is configured to have excellent water tightness, which can effectively prevent water leakage, air leakage, and liquid leakage in underground engineering gaps.

[0143] In a preferred embodiment, the cured flexible sealing layer is configured to achieve a water tightness level of 3 or higher, preferably 4 or higher, and more preferably 5, according to GB / T 7106 testing.

[0144] In a preferred embodiment, the cured flexible sealing layer is configured to have an adhesion strength of ≥2.0 MPa, preferably ≥2.5 MPa, according to GB / T 7124-2008.

[0145] In a preferred embodiment, the cured flexible sealing layer is configured to undergo a tensile test according to GB / T 528-2009 (Type 2 dumbbell, 500±50 mm / min), with a tensile strength ≥3.0 MPa, preferably ≥3.5 MPa.

[0146] In a preferred embodiment, the cured flexible sealing layer is configured to undergo an accelerated aging test according to GB / T 16422.1, and the tensile strength retention rate after 1000h of accelerated aging under ultraviolet irradiation is more than 90%, preferably more than 92%.

[0147] In a preferred embodiment, the cured flexible sealing layer is configured to adapt to a temperature range of -30°C (the low temperature that may occur during energy release) to 150°C (the high temperature during compression heat release) without hardening, softening or decomposing.

[0148] In a preferred embodiment, the composition further comprises an inorganic filler.

[0149] In a preferred embodiment, the composition is a low-permeability heat-resistant composition containing inorganic fillers.

[0150] In a preferred embodiment, the inorganic filler is selected from the group consisting of cement, concrete, geopolymer, desulfurized gypsum, phosphogypsum, quartz powder, silica fume, slag powder, fly ash, or combinations thereof.

[0151] In a preferred embodiment, the inorganic filler is an inorganic filler modified with a silane coupling agent.

[0152] In a preferred embodiment, the inorganic filler is one or more of quartz powder, microsilica powder, flaky mica, and nano clay.

[0153] In a preferred embodiment, the inorganic filler reduces gas permeation and improves heat resistance and dimensional stability through chemical bonding and physical filling.

[0154] In a preferred embodiment, the composition containing inorganic fillers is more suitable for film-forming sealing and filling of airtight weak points in gas storage spaces.

[0155] In a preferred embodiment, the airtight weak points include, but are not limited to, voids or gaps between different interfaces, overlaps of different substrates, and one or more of the following: gaps or channels.

[0156] In a preferred embodiment, the overlap of the different substrates includes one or more of the following: a metal-concrete overlap, a steel-concrete transition zone.

[0157] In a preferred embodiment, the gap channel includes one or more of the following: the root of the through-wall pipe, construction joint, expansion joint, disturbance joint, surrounding rock disturbance fissure zone, and damaged gaps in the lining, surrounding rock, pipe, and casing itself.

[0158] In a preferred embodiment, the voids and cavities between the different interfaces include: voids and cavities between the surrounding rock and the lining, between the primary lining and the secondary lining, between the secondary lining and the free face, between the two layers of casing, and between the casing and the cement ring.

[0159] Sealing and filling methods for compressed air energy storage space This invention provides a method for sealing and filling a compressed air energy storage space, comprising the following steps: (1) Pre-treat the area to be sealed; (2) Apply the composition containing the above polymer emulsion to the part to be sealed, so that the composition seals and / or fills the part to be sealed, and cures the composition to form a flexible sealing material or sealing layer to block or block the leakage channel.

[0160] In a preferred embodiment, in step (1), the pretreatment includes one or more interface treatments such as dust removal, degreasing, and polishing.

[0161] In a preferred embodiment, the part to be sealed is a weak link with poor airtightness, which may include: cracks, joints, porous media, interfaces, voids, cavities, lining interfaces, and sleeve interfaces.

[0162] Specifically, when the gas storage space to be sealed is a tunnel or artificial chamber, the key areas to be sealed include: cracks in the lining, surrounding rock, pipes, and interfaces themselves, or gaps between them and other structures; voids and cavities between the tunnel's open face, arch, primary lining, secondary lining, and surrounding rock.

[0163] When the gas storage space to be sealed is a mine, oil and gas well, gas storage well, or mine roadway, the sealing ratio includes: cracks in the multi-layer casing and cement sheath itself or gaps with other structures; the interface between the casing and the cement sheath; and the annulus between the multi-layer casing.

[0164] In a preferred embodiment, for microcracks or porous media, a pressure grouting or spraying process of 0.5 MPa to 5.0 MPa is used to allow the polymer emulsion in the composition to penetrate deep into the pores due to its low viscosity and small particle size characteristics.

[0165] In a preferred embodiment, for gaps, voids, cavities, etc. between interfaces, a direct filling method is preferred to form a dense sealing layer between the two interfaces to seal and block the parts to be sealed.

[0166] In a preferred embodiment, for the interface between the disturbed fracture zone and the porous lining, a low-solids-content, low-viscosity fine emulsion is first used as a penetrating primer, injected / sprayed under conditions of 0.5 MPa to 5.0 MPa to achieve deep wetting and anchoring; then, a high-solids-content or filler-containing composition is applied as a film-forming topcoat to form a dense, airtight barrier. This process can simultaneously achieve deep sealing and surface airtight film formation, and maintain interface integrity under conditions of alternating temperature and pressure fluctuations.

[0167] In a preferred embodiment, the application includes grouting, spraying, primer coating, and film-forming topcoat.

[0168] In a preferred embodiment, step (2) includes: applying the composition containing the above-mentioned polymer emulsion to microcracks and / or porous media by means of grouting or spraying, so that the composition fills the part to be sealed.

[0169] In a preferred embodiment, the grouting includes pressure grouting, preferably grouting at a pressure of 0.5-5 MPa.

[0170] In a preferred embodiment, step (2) includes: (2-1) The first composition containing the above polymer emulsion is applied to the disturbed fracture zone of the surrounding rock and / or the interface of the porous lining by grouting or spraying to achieve deep wetting and anchoring. (2-2) The second composition containing the above polymer emulsion is applied to the surface to form a film, thereby forming a dense and airtight barrier.

[0171] In a preferred embodiment, the solid content of the first composition is lower than that of the second composition.

[0172] In a preferred embodiment, the solid content of the first composition is between 30% and 60%.

[0173] In a preferred embodiment, the solid content of the second composition is between 50% and 80%.

[0174] In a preferred embodiment, the second composition further includes an inorganic filler.

[0175] In a preferred embodiment, the viscosity of the first composition is lower than that of the second composition.

[0176] Sealed filling structure The present invention provides a sealing and filling structure, comprising a first substrate, a second substrate, and a sealing layer connecting the two; the sealing layer is formed by curing the above composition, and the sealing layer tightly connects the first substrate and the second substrate through siloxane chemical bonding and optional physical anchoring to form a continuous airtight barrier.

[0177] In a preferred embodiment, the first substrate and the second substrate are each independently selected from the group consisting of: metal, concrete, rock, and organic anti-corrosion coating.

[0178] In a preferred embodiment, the metal includes one or more of steel, stainless steel, and iron.

[0179] In a preferred embodiment, the rock mass includes one or more of granite, basalt, and sandstone.

[0180] In a preferred embodiment, the first substrate and the second substrate may be the same or different.

[0181] In a preferred embodiment, the sealing fill structure is a cross-substrate sealing fill structure.

[0182] In a preferred embodiment, the sealing and filling structure maintains a sealed and tightly bonded state during periodic expansion and contraction deformation and / or pressure fluctuations, without deformation or cracking, thus meeting the requirements for long-term cycle life.

[0183] In a preferred embodiment, the pressure fluctuation is a pressure fluctuation of 6 MPa to 25 MPa.

[0184] In the steel-concrete transition zone or at the metal-concrete-coating overlap, the above composition is used to form a sealing layer across the interface between the first and second substrates. The sealing layer connects the two substrates through siloxane chemical bonds and optional physical anchoring, forming a continuous airtight barrier that adapts to periodic expansion and contraction deformation.

[0185] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. In the embodiments, a total weight of 100 parts by weight of octyl acrylate and styrene is used as the basis for calculation. Unless otherwise stated, percentages and parts are weight percentages and parts by weight.

[0186] Material Pluronic® F127 was purchased from BASF, and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane was purchased from Gelest.

[0187] Example 1: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (60 parts by weight), styrene (40 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (1 part by weight) was added to a deionized aqueous solution containing Pluronic® F127 EO-PO-EO block copolymer (3 parts by weight) under stirring to form a stable pre-emulsion. The pre-emulsion was then processed twice under a high-pressure homogenizer at 50 MPa to obtain droplet D. 50 A pre-emulsion with a PDI of 720 nm (PDI = 0.12) was obtained. Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, the sodium persulfate solution (0.1 parts by weight) was added dropwise over 7 hours. A polymer emulsion (40% solids content) with a Tg of -9°C was obtained.

[0188] Example 2: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (40 parts by weight), styrene (60 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (1 part by weight) was added to a deionized aqueous solution containing Pluronic® F127 EO-PO-EO block copolymer (3 parts by weight) under stirring to form a stable pre-emulsion. The pre-emulsion was then processed twice under a high-pressure homogenizer at 50 MPa to obtain droplet D. 50 A pre-emulsion with a PDI of 720 nm (PDI = 0.12) was obtained. Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, the sodium persulfate solution (0.1 parts by weight) was added dropwise over 7 hours. A polymer emulsion (40% solids content) with a Tg of 20°C was obtained.

[0189] Example 3: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (50 parts by weight), styrene (50 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (1 part by weight) was added to a deionized aqueous solution of Pluronic® F127 EO-PO-EO block copolymer (3 parts by weight) under stirring to form a stable pre-emulsion. The pre-emulsion was homogenized twice at 50 MPa to obtain a droplet D50 of 720 nm (PDI = 0.12). Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, the sodium persulfate solution (0.1 parts by weight) was added dropwise over 7 hours. A polymer emulsion (40% solids content) with a Tg of 7°C was obtained.

[0190] Example 4: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (50 parts by weight), styrene (50 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (1 part by weight) was added to a deionized aqueous solution containing Pluronic® F127 EO-PO-EO block copolymer (5 parts by weight) under stirring to form a stable pre-emulsion. The pre-emulsion was then processed twice under a high-pressure homogenizer at 50 MPa to obtain droplet D. 50 A pre-emulsion with a Tg of 620 nm (PDI = 0.09) was obtained. Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, the sodium persulfate solution (0.1 parts by weight) was added dropwise over 7 hours. A polymer emulsion (40% solids content) with a Tg of 7°C was obtained.

[0191] Example 5: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (50 parts by weight), styrene (50 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (1 part by weight) was added to a deionized aqueous solution containing Pluronic® F127 EO-PO-EO block copolymer (3 parts by weight) under stirring to form a stable pre-emulsion. The mixture was then processed twice under a high-pressure homogenizer at 100 MPa to obtain droplet D. 50 A pre-emulsion with a Tg of 580 nm (PDI = 0.11) was obtained. Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, the sodium persulfate solution (0.1 parts by weight) was added dropwise over 7 hours. A polymer emulsion (40% solids content) with a Tg of 7°C was obtained.

[0192] Example 6: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (50 parts by weight), styrene (50 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (1 part by weight) was added to a deionized aqueous solution containing Pluronic® F127 EO-PO-EO block copolymer (3 parts by weight) under stirring to form a stable pre-emulsion. The pre-emulsion was then processed twice under a high-pressure homogenizer at 150 MPa to obtain droplet D. 50 A pre-emulsion with a Tg of 510 nm (PDI = 0.13) was obtained. Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, the sodium persulfate solution (0.1 parts by weight) was added dropwise over 7 hours. A polymer emulsion (40% solids content) with a Tg of 7°C was obtained.

[0193] Example 7: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (50 parts by weight), styrene (50 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (1 part by weight) was added to a deionized aqueous solution containing Pluronic® F127 EO-PO-EO block copolymer (5 parts by weight) under stirring to form a stable pre-emulsion. The pre-emulsion was then processed twice under a high-pressure homogenizer at 100 MPa to obtain droplet D. 50 A pre-emulsion with a PDI of 470 nm (PDI = 0.09) was obtained. Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, the sodium persulfate solution (0.1 parts by weight) was added dropwise over 7 hours. A polymer emulsion (40% solids content) with a Tg of 7°C was obtained.

[0194] Example 8: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (50 parts by weight), styrene (50 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (1 part by weight) was added to a deionized aqueous solution containing Pluronic® F127 EO-PO-EO block copolymer (5 parts by weight) under stirring to form a stable pre-emulsion. The pre-emulsion was then processed twice under a high-pressure homogenizer at 100 MPa to obtain droplet D. 50 A pre-emulsion with a PDI of 470 nm (PDI = 0.09) was obtained. Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, the sodium persulfate solution (0.1 parts by weight) was added dropwise over 5 hours. A polymer emulsion (40% solids content) with a Tg of 7°C was obtained.

[0195] Example 9: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (50 parts by weight), styrene (50 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (1 part by weight) was added to a deionized aqueous solution containing Pluronic® F127 EO-PO-EO block copolymer (5 parts by weight) under stirring to form a stable pre-emulsion. The pre-emulsion was then processed twice under a high-pressure homogenizer at 100 MPa to obtain droplet D. 50 A pre-emulsion with a PDI of 470 nm (PDI = 0.09) was obtained. Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, a sodium persulfate solution (0.15 parts by weight) was added dropwise over 6 hours. A polymer emulsion (40% solids content) with a Tg of 7°C was obtained.

[0196] Example 10: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (50 parts by weight), styrene (50 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (3 parts by weight) was added to a deionized aqueous solution containing Pluronic® F127 EO-PO-EO block copolymer (5 parts by weight) under stirring to form a stable pre-emulsion. The pre-emulsion was then processed twice under a high-pressure homogenizer at 100 MPa to obtain droplet D. 50 A pre-emulsion with a PDI of 470 nm (PDI = 0.09) was obtained. Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, a sodium persulfate solution (0.15 parts by weight) was added dropwise over 6 hours. A polymer emulsion (40% solids content) with a Tg of 7°C was obtained.

[0197] Example 11: Preparation of fine emulsion polymers A monomer mixture consisting of octyl acrylate (50 parts by weight), styrene (50 parts by weight), and N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane (5 parts by weight) was added to a deionized aqueous solution containing 5 parts by weight of Pluronic® F127 EO-PO-EO block copolymer under stirring to form a stable pre-emulsion. The pre-emulsion was then processed twice under a high-pressure homogenizer at 100 MPa to obtain droplet D. 50 A pre-emulsion with a PDI of 470 nm (PDI = 0.09) was obtained. Subsequently, under nitrogen protection at 75°C, a sodium persulfate solution (0.1 parts by weight) was added to the reactor. After 10 minutes, a sodium persulfate solution (0.15 parts by weight) was added dropwise over 6 hours. A polymer emulsion (40% solids content) with a Tg of 7°C was obtained.

[0198] Example 12 Adhesion performance The polymer emulsions in Examples 1-11 are mixed with cement, powder fillers, and water to prepare engineering materials for bonding steel plates, glass, concrete, etc.

[0199] 1. Detailed description of the experimental procedure (1) Tensile shear test of rigid materials (steel plate, glass) – according to GB / T 7124 (ISO 4587) This test aims to simulate the ability of the bonded interface to resist shear failure when a structural member is subjected to axial load.

[0200] Specimen preparation: according to GB / T 7124 Figure 1The design drawings specify the shape and size of the sample. Specifically, a standard steel plate with a specification of 100mm×25mm×1.6mm and tempered glass of the same thickness are selected.

[0201] Surface treatment: The steel plate surface is sandblasted and degreased with acetone; the glass substrate is cleaned and dried according to standards to ensure that no contaminants affect the interface wetting.

[0202] Overlap method: A single overlap is used, with an overlap length of 12.5mm ± 0.25mm. The bonding area A = 12.5 × 25 = 312.5mm². 2 .

[0203] Loading conditions: Use a tensile testing machine equipped with constant rate control, and adjust the loading rate to a shear stress change rate of 8.3 MPa / min ~ 9.8 MPa / min.

[0204] Test environment: temperature (23±2)℃, relative humidity (50±5)%.

[0205] (2) Tensile bond properties test of concrete substrate - according to GB / T 13477.8 (ISO 8339) Specimen preparation: Substrate: prepared according to GB / T 13477.8 Figure 1 The design drawings specify the shape and size of the test specimen. Specifically, two parallel standard cement mortar / concrete substrate blocks with dimensions of 75mm × 62mm × 12mm are used.

[0206] Filling dimensions: Inorganic adhesive is embedded between two substrates to form an adhesive body with a cross-section of 12mm × 12mm and a length of 50mm. The calculated bonding area S = 12 × 50 = 600 mm². 2 .

[0207] Loading conditions: The tensile testing machine was used to stretch the specimen at a speed of (5.5±0.7) mm / min at (23±2)℃ until the specimen failed.

[0208] 2. Experimental Results and Numerical Calculations Based on the failure load measured in the experiment, the bond strength index of each substrate is calculated.

[0209] (1) Quantitative calculation process Shear strength of steel plate (τ): Failure load F = 1193.75 N Glass shear strength (τ): failure load F = 1065.63 N Maximum tensile strength of concrete (T)s Maximum tensile force P = 1890 N (2) Summary table of test data The results are shown in Table 1 and Figure 1 As shown.

[0210] Table 1 Example 13 Tensile Properties The polymer emulsions in Examples 1-11 were mixed with cement, powder fillers, and water to form engineering materials, which were then cured to form specimens of fixed size and shape for testing their tensile properties, in accordance with the standard GB / T 528-2009.

[0211] 1. Experimental Procedure Sample preparation: Sample type: Type 2 dumbbell-shaped sample.

[0212] Specifications: The width (W) of the narrow part of the sample is 4.0 mm, the gauge length (L0) is 20 mm, and the thickness (t) is adjusted to (2.0±0.2) mm.

[0213] Environmental conditioning: The sample shall be conditioned at a standard laboratory temperature of (23±2)℃ for no less than 16 hours.

[0214] Testing steps: The cross-sectional area of ​​the narrow section of the sample (S=W⋅t) is accurately measured using a thickness gauge.

[0215] The specimen is symmetrically clamped on the tensile testing machine fixture, and the tensile speed is set to 500 mm / min.

[0216] Start the instrument until the sample breaks, and record the maximum force (F) at the moment of fracture. b and the displacement length between gauge lengths (L) b ).

[0217] 2. Experimental Results The results are shown in Table 2 and Figure 2: Table 2 Example 14 Air tightness test The polymer emulsions in Examples 1-11 were mixed with cement, powder fillers, and water to prepare a sealing material for verifying its airtightness, based on the standard GB / T31433-2015.

[0218] 1. Specimen Description A high-performance aluminum alloy casement window, wherein the sealing system of the glass and frame, and the sash and frame, uses a sealant containing the polymer emulsion of the present invention.

[0219] 2. Quantitative performance (based on test results from GB / T 7106-2019) A representative window specimen (area 1.8m²) equipped with this sealing system 2 In the test (with an opening seam length of 5.6m), its quantitative indicators performed as follows: Air permeation per unit seam length ( q 1 After pressure pulse preprocessing and linear regression calculation under a 10Pa pressure difference, the measured value was 0.74m. 3 / (m·h) Air infiltration rate per unit area ( q 2 The measured converted value is 2.3 m. 3 / (m 2 ·h).

[0220] Air tightness rating: According to the grading standard of "General Technical Conditions for Building Curtain Walls, Doors and Windows" (GB / T 31433-2015), the air tightness performance of this system is clearly determined to be level 7.

[0221] Example 15 Water tightness The polymer emulsions in Examples 1-11 were mixed with cement, powder fillers, and water to prepare a sealing material for verifying its airtightness, based on the standard GB / T 7106.

[0222] 1. Experimental preparation and apparatus Test specimen description: A high-performance aluminum alloy casement window with an area of ​​A = 2.4m² was used, equipped with this sealant. 2 .

[0223] Testing environment: Indoor temperature 20℃, relative humidity 50%.

[0224] Sprinkler system: Sprinkler flow rate set at the standard requirement of 3.0 L / m 2 ·min.

[0225] 2. Test Procedure: Fluctuating Pressure Method (according to Clause 8.4 of GB / T 7106) To demonstrate the material's stability under extreme weather conditions, this experiment employed a more stringent fluctuating pressure method.

[0226] Preparatory pressurization: Apply three pressure pulses with an absolute pressure difference of 500 Pa.

[0227] Fluctuation detection: Water spraying stage: Start the water spraying system to spray the specimen evenly for 10 minutes.

[0228] Staged pressurization: Pressurize step by step according to the pressurization sequence diagram in Figure 5 and the pressurization sequence table in Table 2 of GB / T 7106, Clause 8.4.

[0229] Fluctuation parameters: The duration of the fluctuating pressure is 15 minutes or until leakage occurs. The fluctuation amplitude is 0.5 times the average value, and the period is 3-5 seconds.

[0230] Leakage observation: Technicians continuously observe the inside of the test specimen and record whether water droplets fall or there is continuous seepage.

[0231] 3. Experimental Results and Numerical Calculations (1) Experimental Record Sheet The order of pressure fluctuations and leakage status are shown in Table 3 below.

[0232] Table 3 (2) Calculation and judgment (based on GB / T 7106, Clause 8.5.1) According to the grading principle of GB / T 7106-2019, the pressure difference of the previous level of leakage pressure difference shall be used as the test value of water tightness performance.

[0233] (3) Grading determination (refer to Table 16 of GB / T 31433-2015) The water tightness results of the sealant containing the polymer emulsion of the present invention are shown in Table 4 below.

[0234] Table 4 4. Conclusion: Engineering Value Evaluation of Sealants The test results show that the performance has been significantly improved: In this test, the structural components using sealant successfully passed the fluctuating pressure test with an average value of 500 Pa (peak value of 750 Pa) and were ultimately rated as level 5.

[0235] As can be seen from the above, the rating result far exceeds the Class 3 standard required for general engineering projects, proving that the sealing material can meet the requirements of extreme watertightness.

[0236] In watertightness tests, the value of sealing materials lies in the reliability of their interfacial adhesion and fatigue resistance. The sealing material made from the polymer emulsion of this invention exhibits superior weather resistance and chemical stability, and is less prone to degradation or debonding under continuous spraying and dynamic wind pressure fluctuations. Watertightness failure typically stems from pressure differences forcing moisture into the room through tiny cracks. This sealing material, through its extremely strong interfacial wettability and permeability, forms a "zero-gap" structural seal, thus maintaining both airtightness and watertightness even under high-pressure fluctuations.

[0237] Example 16 Aging Resistance The polymer emulsions in Examples 1-11 were mixed with cement, powder fillers, and water to prepare engineering materials, which were then cured and used to test their aging resistance.

[0238] 1. Review and continuation of experimental conditions Test standards: GB / T 16422.1 and GB / T 16422.3.

[0239] Light source and circulation: A UVA-340 (Type 1A) fluorescent ultraviolet lamp was used, with 8 hours of irradiation (60℃, 0.76W / (m²)). 2 The process alternates between ⋅nm) and 4h condensation (50℃).

[0240] Testing indicators: Tensile strength, elongation at break, and color difference ΔE are tested according to ISO 4582. * and surface morphology.

[0241] 2. Experimental Results The results are shown in Table 5 and Figure 3 below. It can be seen that the engineering materials modified by the polymer emulsion of the present invention have excellent aging resistance. The strength is still maintained at more than 93% within an ultra-long period of 10,000 hours.

[0242] Table 5 All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. Use of a composition, characterized in that, For compressed air energy storage, the composition forms a closed gas storage space by sealing and / or filling. The composition comprises a polymer emulsion containing polymer particles dispersed in an aqueous phase, wherein the polymer particles are copolymerized from acrylate monomers, styrene monomers and silane monomers containing hydrophobic long chains in the presence of a hydrophobic stabilizer.

2. The use as described in claim 1, characterized in that, When the composition is applied to the gas storage space, it solidifies to form a cross-linked network containing Si-O-Si bonds, forming a flexible sealing material or sealing layer and achieving adhesive sealing.

3. The use as described in claim 1, characterized in that, The sealing and / or filling is to form a flexible, airtight, dense, continuous sealing material or sealing layer between the same substrate or across substrates.

4. The use as described in claim 3, characterized in that, The substrate is selected from the group consisting of: metal, concrete, rock, and organic anti-corrosion coating.

5. The use as described in claim 1, characterized in that, The gas storage space is an underground enclosed / semi-enclosed space, including mines, subsea gas tanks, caves, oil and gas wells, gas storage wells, tunnels, artificial chambers, urban underground spaces, or mine roadways.

6. The use as described in claim 1, characterized in that, The polymer emulsion is prepared by the following method, including the following steps: (s1) Mix conventional monomers with functional monomers, and then add a primary emulsifier solution to obtain a pre-emulsion; The functional monomer serves as a stabilizer, a silane coupling agent, and a reactive monomer, possessing a triple function of "stabilizing / polymerizable / coupling," and is N-(3-methacryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane. (s2) The pre-emulsion obtained in step (s1) is homogenized and mixed to obtain a pre-emulsion; (s3) The pre-emulsion obtained in step (s2) is mixed with an initiator and subjected to a fine emulsion polymerization reaction to obtain the fine emulsion polymer.

7. The use as described in claim 6, characterized in that, The conventional monomers include octyl acrylate and styrene.

8. A method for sealing a compressed air energy storage space, characterized in that, Includes the following steps: (1) Pre-treat the area to be sealed; (2) Applying a composition containing a polymer emulsion to the area to be sealed, thereby sealing and / or filling the area to be sealed, and curing to form a flexible sealing material or sealing layer to block or block the leakage area; The polymer emulsion contains polymer particles dispersed in an aqueous phase. The polymer particles are formed by copolymerization of acrylate monomers, styrene monomers and silane monomers containing hydrophobic long chains in the presence of a hydrophobic stabilizer.

9. The method as described in claim 8, characterized in that, Step (2) includes the following steps: A composition containing a polymer emulsion is applied to microcracks and / or porous media by means of grouting, spraying and / or scraping, so that the composition seals the microcracks and / or porous media; Step (2) includes the following steps: A composition containing a polymer emulsion is injected directly between two interfaces where there are voids, cavities, or annular spaces to form a dense sealing layer and seal the gas storage space.

10. A sealing and filling structure, characterized in that, It includes a first substrate, a second substrate, and a sealing layer connecting the two; the sealing layer is formed by curing a composition containing a polymer emulsion, and the sealing layer tightly connects the first substrate and the second substrate through siloxane chemical bonding and optional physical anchoring to form a continuous airtight barrier; The polymer emulsion contains polymer particles dispersed in an aqueous phase. The polymer particles are formed by copolymerization of acrylate monomers, styrene monomers and silane monomers containing hydrophobic long chains in the presence of a hydrophobic stabilizer.

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